Patent GB-774663-A (GB)
Title: Polyglycidyl ethers of tetraphenols
IPC: C07D301/28
Filed: 1955-10-31
Abstract: Polyglycidylethers of tetraphenols having two hydroxyaryl groups at each end of an aliphatic chain are prepared by reacting such a phenol with epichlorhydrin or dichlorhydrin in a ratio of 2-10 mol. chlorhydrin per phenolic hydroxyl group in the presence of an alkalimetalhydroxide which is added gradually to a boiling mixture of the reactants. Tetraphenols specified are 1,1,2,2-tetrakis-(hydroxyphenyl) ethane; 1,1,3,3-tetrakis-(hydroxyphenyl) propane etc.; halogen substituted phenols may also be used, e.g. 1,1,3,3-tetrakis-(hydroxyphenyl) - 2 - chloro - propane &c. and phenols having substituted hydroxyphenyl groups and polynuclear hydroxyphenyl groups, e.g. 1,1,2,2-tetrakis - (2 - hydroxy - 5 - methylphenyl) ethane; 1,1,3,3 - tetrakis - (4 - hydroxy - 2,6-ditertiarybutylphenyl) propane; 1,1,6,6-tetrakis - (3 - chloro - 4 - hydroxyphenyl) hexane; and 1,1,4,4 - tetrakis - (2 - hydroxynaphthyl) butane. The phenols may be prepared by reacting a phenol with an ethylenic ether. The polyglycidyl ethers are solid resins at 25 DEG C. and are soluble in lower aliphatic ketones and mixtures of these with aromatic hydrocarbons. They are curable by addition of dicyandiamide, mono or polyamines or polycarboxylic acids; they may be mixed with fillers, pigments, plasticizers, monoepoxy compounds and phenolic, urea, and melamine resins. In Examples (1), 173 parts of 1,1,2,2-tetrakis - (hydroxyphenyl) ethane were reacted with 1610 parts epichlorhydrin in presence of 70 parts NaOH in 82 parts water added at such a rate to keep the reflux temperatures at 103-107 DEG  C.ALSO:Tetraphenols having 2 hydroxyaryl groups at each end of an aliphatic hydrocarbon chain are produced by reacting an a ,b -ethylenic ether with a phenol which has at least one replaceable hydrogen atom attached to the ring to which the phenolic group is linked.  In this reaction the bond linking the ether oxygen atom to the ethylenic carbon atom is opened and two hydroxy aryl groups corresponding to the phenol used become linked directly by C-C bonds to the C atom of the ether set free. Simultaneously the other carbon atom to which the ether oxygen was attached in the starting ether becomes linked to by two hydroxyaryl groups.  Tetrakis (hydroxyaryl) alkane compounds may be obtained from a ,b -diethylenic ethers in accordance with the equation: <FORM:0774663/IV(b)/1> The same type of product is obtained with monoethylenic ethers in which the saturated C atom to which the ether O atom is attached is linked directly to a divalent atom of a nonmetallic element of Group VI, e.g. oxygen, sulphur, selenium or tellurium.  In preparing the tetraphenols at least 0.2 mol. of acid should be used per mol. ethylenic ether employed and 2-10 mols. phenol per mol. ether; the reaction is exothermic and may be activated by addition of mercaptans.  The following tetraphenols are specified: 1,1,2,2 - tetrakis - (hydroxyphenyl) ethane; 1,1,3,3 - tetrakis - (hydroxyphenyl) propane; 1,1,4,4 - tetrakis - (hydroxyphenyl) butane; 1,1,5,5 - tetrakis - (hydroxyphenyl)-3 - methylpentane; 1,1,4,4 - tetrakis - (hydroxyphenyl) - 2 - ethylbutane; 1,1,8,8 - tetrakis-(hydroxyphenyl octane; 11,10,10 - tetrakis-(hydroxyphenyl) decane; 1,1,3,3 - tetrakis-(hydroxyphenyl) - 2 - chlorpropane; 1,1,4,4-tetrakis - (hydroxyphenyl) - 2,3 - dibromobutane; 1,1,6,6 - tetrakis - (hydroxyphenyl) hexanol - 2; 1,1,2,2 - tetrakis - (2 - hydroxy - 5-methylphenyl) ethane; 1,1,3,3 - tetrakis - (4-hydroxy - 2,6 - detertiarybutylphenyl) propane; 1,1,6,6 - tetrakis - (3 - chloro - 4 - hydroxyphenyl) hexane; 1,1,4,4 - tetrakis-(2 - hydroxynaphthyl) butane.  The tetraphenols are used in reacting with epihalohydrin to obtain epoxy resins.